The first systematic and rational approaches for controlling the stereochemistry and substitution pattern of hydroxyl and amino substituents in the stereoselective synthesis of polyhydroxylated/polyaminated hydrocarbons are described. The cornerstone of these approaches is to develop two key synthetic methodologies, the positional-/regio-selective asymmetric aminohydroxylation (AA) reaction of conjugated dienes and the Lewis acid-mediated Aldol addition reaction between silyloxydienes and a,b-hydroxyaminated/a,b-diaminated aldehydes/imines. The former methodology is a logical extension of our substrate-directed approach for the regioselective AA reaction of olefins to the conjugated diene systems. a,b-Hydroxyaminated/a,b-diaminated aldehydes/imines required for the latter methodology can be readily prepared through the regioselective AA reaction of appropriate olefins. The two proposed methodologies can generate four contiguous chiral centers with hydroxyl and amino substituents in a highly stereocontrolled manner, and are complementary to each other. The two methodologies can also provide succinct ways for controlling the substitution pattern of the hydroxyl and amino groups at the corresponding four chiral centers. Thus, they can provide a unified and general solution for controlling the stereochemistry and substitution pattern of hydroxyl and amino substituents in the stereoselective synthesis of polyhydroxylated/polyaminated hydrocarbons (see Schemes 4 & 7). Generality and practicality of these two synthetic methodologies are demonstrated in the stereoselective syntheses of sphingosines, phytosphingosines, sphingofungins, C2-symmetric 1,4-diamino-2,3-diols, alexines, australines, and casuarines, which have been shown to exhibit a variety of biological activities such as antiviral, antifungal, and antitumor activities. In addition to the positional-/regio-selective AA reaction of conjugated dienes and the Lewis acid-mediated AIdol addition reaction between silyloxydienes and a,b-hydroxyaminated/a,b-diaminated aldehydes/imines, the ring-closing olefin metathesis reaction as well as diastereoselective epoxidation and dihydroxylation reactions will be used as key steps in the proposed stereoselective synthesis of the target compounds. Our proposed stereoselective syntheses can generate all stereogenic centers in the target compounds in a highly regio-/stereo-controlled manner. The proposed syntheses are very divergent and flexible in such a way that different target compounds (or isomers of a given target compound) can be derived from common starting olefins, conjugated dienes, and/or intermediates. All target compounds are synthesized from readily available achiral olefins and conjugated dienes by almost the same synthetic routes. Therefore, our proposed synthetic methodologies can provide most comprehensive solutions for the stereoselective synthesis of these classes of compounds. Furthermore it can be envisioned that other polyhydroxylated/polyaminated hydrocarbons as well as other derivatives of our target compounds can also be synthesized by slight modifications of our proposed methodologies.